CN117985779A - Sodium ion battery anode material precursor, preparation method and application - Google Patents

Sodium ion battery anode material precursor, preparation method and application Download PDF

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Publication number
CN117985779A
CN117985779A CN202410167092.6A CN202410167092A CN117985779A CN 117985779 A CN117985779 A CN 117985779A CN 202410167092 A CN202410167092 A CN 202410167092A CN 117985779 A CN117985779 A CN 117985779A
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precursor
carbonate
ion battery
positive electrode
sodium ion
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徐学留
阮丁山
刘更好
李永光
胡蝶
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a sodium ion battery positive electrode material precursor, a preparation method and application, wherein the main component of the sodium ion battery positive electrode material precursor is a carbonate precursor, a small amount of hydroxide precursor is also introduced, the introduction of the hydroxide precursor is beneficial to controlling the particle size distribution of the precursor in the precursor preparation process, narrowing the particle size distribution of the carbonate precursor and further improving the tap density of the precursor; meanwhile, a small amount of hydroxide precursor is introduced in the process of preparing the precursor to serve as seed crystal, so that the particle size distribution of the carbonate precursor is narrowed, the sphericity of the precursor is improved, and the precursor material with small specific surface area and good fluidity is obtained.

Description

Sodium ion battery anode material precursor, preparation method and application
Technical Field
The disclosure relates to the technical field of sodium ion battery layered oxide positive electrode material precursors, and in particular relates to a sodium ion battery positive electrode material precursor, a preparation method and application.
Background
Common positive electrode materials of the sodium ion battery comprise Prussian white, phosphate polyanions, multi-element layered oxides and the like, wherein the multi-element layered oxides have ideal specific capacity, are easy to synthesize and have cyclic stability, and have certain potential advantages as the positive electrode materials of the sodium ion battery, so that the positive electrode materials are widely researched and developed.
The layered sodium oxide positive electrode material consists of a plurality of metal ions, wherein the metal ions have good coordination and complementation effects, and part of valence-variable metal ions, such as Cu ions, improve the air stability of the material; however, for copper-based multi-component hydroxide precursors, the precipitation rate is inconsistent due to the difference of Cu ions KSP and other ions, so that segregation phenomenon occurs, uniform precipitation is difficult, and the performance and industrialization of the synthetic material are seriously affected.
In the sodium ion battery material, the carbonate precursor has the advantages of high tap density and low cost, and the carbonate route can be used for replacing the hydroxide route, but the carbonate precursor also has some problems, such as poor synthesis process stability, excessively high growth speed, difficult control of particle size, non-uniform particle size distribution and the like.
In view of this, the present disclosure is specifically proposed.
Disclosure of Invention
The invention aims to provide a precursor of a positive electrode material of a sodium ion battery, a preparation method and application, and the precursor has higher tap density.
The present disclosure is implemented as follows:
In a first aspect, the present disclosure provides a sodium ion battery cathode material precursor comprising a first precursor particle and a second precursor particle, the first precursor particle being a carbonate precursor, the second precursor particle comprising a core and a shell, the core being a hydroxide precursor, the shell being a carbonate precursor.
In some embodiments, the hydroxide precursor comprises 2% -20% of the total mass of the sodium ion battery cathode material precursor.
In some embodiments, the sodium ion battery positive electrode material precursor D50 is 5 μm to 20 μm.
In some embodiments, the D50 of the core is 2 μm to 8 μm.
In some embodiments, the metal element in the carbonate precursor and/or hydroxide precursor is one or a combination of two or more of Li, K, al, ti, cr, mn, fe, cu, co, ni, zn, sn, zr, mo, nb, Y, W, in, ge.
In a second aspect, the present disclosure provides a method for preparing a precursor of a positive electrode material of a sodium ion battery according to any one of the preceding embodiments, wherein in the process of preparing the carbonate precursor particles by adopting the coprecipitation method, the hydroxide precursor is used as a seed crystal, and the particle size distribution of the carbonate precursor particles is adjusted, so as to obtain the precursor of the positive electrode material of the sodium ion battery.
In some embodiments, in the process of preparing carbonate precursor particles by adopting the coprecipitation method, each time the obtained precipitate D50 reaches a preset particle size, the seed crystal is added into the reaction system, and the total mass fraction of the seed crystal in the sodium ion battery positive electrode material precursor is 2% -20%.
In some embodiments, the method comprises: and (3) adding the salt solution and the carbonate solution of the metal element into the base solution in parallel, performing coprecipitation reaction, and adding the seed crystal into the reaction system in batches each time the precipitated D50 reaches the preset particle size.
In some embodiments, further comprising running ammonia into the base liquid.
In some embodiments, the ammonia concentration in the reaction solution is maintained between 0.1g/L and 8g/L during the co-precipitation reaction.
In some embodiments, the total concentration of the metal elements in the salt solution of the metal elements is 0.1mol/L to 2.5mol/L.
In some embodiments, the total concentration of the metal elements in the salt solution of the metal elements is 1.7mol/L to 2.0mol/L.
In some embodiments, the salt solution flow acceleration of the metal element is 1L/h to 20L/h.
In some embodiments, the carbonate solution has a concentration of 0.1mol/L to 1.8mol/L.
In some embodiments, the carbonate solution has a concentration of 1.5mol/L to 1.8mol/L.
In some embodiments, the carbonate solution has a flow acceleration of 8L/h to 12L/h.
In some embodiments, the base fluid further comprises ammonia water, and the concentration of ammonia in the base fluid is 0g/L to 8g/L.
In some embodiments, the base fluid further comprises carbonate, wherein the concentration of carbonate in the base fluid is from 0.01mol/L to 1.5mol/L.
In some embodiments, the coprecipitation reaction is carried out under inert gas protection.
In some embodiments, the pH of the coprecipitation step is 8 to 11.
In some embodiments, the temperature of the coprecipitation reaction is from 30 ℃ to 70 ℃.
In some embodiments, the coprecipitation reaction is carried out under stirring conditions at a frequency of 30Hz to 60Hz.
In some embodiments, the seed crystals are added in portions over 2h-5 h.
In some embodiments, further comprising the preparation of seed crystals: and (3) introducing ammonia water into the salt solution of the metal element, adjusting the pH value of the reaction solution by adopting alkali liquor, and synthesizing the seed crystal.
In some embodiments, the ammonia concentration in the reaction solution is maintained at 2g/L to 4g/L during the seed crystal preparation step.
In some embodiments, the seed crystal is prepared by maintaining the pH of the reaction solution in the range of 8-13.
In some embodiments, the seed crystal is prepared at a step temperature of 30 ℃ to 70 ℃.
In some embodiments, the lye is a sodium hydroxide solution or a potassium hydroxide solution, and the lye concentration is 5mol/L to 10mol/L.
In some embodiments, the seed crystal preparation step is performed under stirring conditions at a frequency of 30Hz to 60Hz.
In a third aspect, the present disclosure provides a positive electrode material obtained by mixing and sintering the sodium ion battery positive electrode material precursor according to any one of the foregoing embodiments with a sodium source.
In a fourth aspect, the present disclosure provides a positive electrode sheet, including the positive electrode material described in the foregoing embodiment.
In a fifth aspect, the present disclosure provides a sodium ion battery comprising the positive electrode sheet of the foregoing embodiment.
The present disclosure has the following beneficial effects:
The sodium ion battery positive electrode material precursor comprises a carbonate precursor and a hydroxide precursor, the introduction of the hydroxide precursor is beneficial to controlling the particle size distribution of the precursor in the precursor preparation process, narrowing the particle size distribution of the carbonate precursor and further improving the tap density of the precursor; meanwhile, a small amount of hydroxide precursor is introduced in the process of preparing the precursor to serve as seed crystal, so that the particle size distribution of the carbonate precursor is narrowed, the sphericity of the precursor is improved, and the precursor material with small specific surface area and good fluidity is obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is an electron micrograph of a carbonate precursor of Ni 0.3Mn0.50Fe0.1Cu0.1CO3 obtained in example 1;
FIG. 2 is an electron micrograph of a carbonate precursor of Ni 0.3Mn0.50Fe0.1Cu0.1CO3 obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the disclosure provides a sodium ion battery positive electrode material precursor, which comprises first precursor particles and second precursor particles, wherein the first precursor particles are carbonate precursors, the second precursor particles comprise a core and a shell, the core is a hydroxide precursor, and the shell is a carbonate precursor.
The main component of the precursor of the sodium ion battery positive electrode material in the embodiment is a carbonate precursor, a small amount of hydroxide precursor is also introduced, the introduction of the hydroxide precursor is beneficial to controlling the particle size distribution of the precursor in the precursor preparation process, narrowing the particle size distribution of the carbonate precursor, further improving the tap density and sphericity of the precursor, improving the cycling stability of the prepared positive electrode material and the like.
In the present embodiment, the metal elements in the hydroxide precursor and the carbonate precursor may be metal elements suitable for use in the positive electrode material of the sodium ion battery, and one or two or more metal elements may be used, and in order to improve the performance of the positive electrode material, generally, two or more metal elements are selected; the metal elements in the hydroxide precursor and the carbonate precursor may be the same or different, and in general, the same metal element is selected for the hydroxide precursor and the carbonate precursor.
In some embodiments, the hydroxide precursor accounts for 2% -20% of the total mass of the sodium ion battery positive electrode material precursor, specifically may be 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 5%, 10%, 15%, 20% or any value between 2% -20%, any value between 2% -3%, and if the hydroxide precursor accounts for too little, the effect of improving the particle size distribution is poor; if the ratio of the hydroxide precursor is too large, the overall performance of the sodium ion battery positive electrode material precursor in the present embodiment may be affected by the problem of easy segregation and the like of the hydroxide precursor itself.
In some embodiments, the precursor D50 of the positive electrode material of the sodium ion battery is 5 μm to 20 μm, specifically may be any value between 5 μm, 8 μm, 11 μm, 14 μm, 17 μm, 20 μm or 5 μm to 20 μm, and the introduction of the hydroxide precursor is advantageous for obtaining carbonate precursor particles with smaller particle size, and if the precursor of the positive electrode material has smaller particle size, the particle size distribution range is smaller, and the effect of narrowing the particle size distribution after adding the hydroxide is relatively smaller.
In some embodiments, the D50 of the core is between 2 μm and 8 μm, specifically may be any value between 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, or 2 μm and 8 μm, and the introduction of the hydroxide precursor having a smaller particle size may allow the carbonate precursor generated during co-precipitation to grow gradually on the hydroxide precursor, thereby inhibiting the continued growth of the carbonate precursor particles.
In some embodiments, the metal element in the carbonate precursor and/or hydroxide precursor is one or more than two of Li, K, al, ti, cr, mn, fe, cu, co, ni, zn, sn, zr, mo, nb, Y, W, in, ge, specifically, a combination of Mn, fe, co, ni metal elements, a combination of three elements of Mn, fe and Cu, or other combinations.
Another embodiment of the present disclosure provides a method for preparing a precursor of a positive electrode material of a sodium ion battery according to any one of the preceding embodiments, including: in the process of preparing carbonate precursor particles by adopting a coprecipitation method, hydroxide precursors are used as seed crystals, and the particle size distribution of the carbonate precursor particles is regulated to obtain the sodium ion battery anode material precursor.
In the embodiment, in the process of preparing carbonate precursor particles by adopting a coprecipitation method, small particle seed crystals with the particle size smaller than D50 are added into a coprecipitation system, and a hydroxide precursor is used as seed crystals, so that the carbonate precursor can be preferentially precipitated on the surface of the hydroxide precursor, and further, the excessive rapid and excessive growth of the carbonate precursor particles can be avoided, the particle size distribution of the carbonate is effectively narrowed, the stability of the preparation process is improved, and meanwhile, the small particle carbonate precursor can be synthesized, so that the obtained precursor has high tap density, high sphericity, good fluidity and small specific surface area.
In some embodiments, in the process of preparing carbonate precursor particles by adopting the coprecipitation method, each time the obtained precipitate D50 reaches a preset particle size, the seed crystal is added into the reaction system, and the total mass fraction of the seed crystal in the sodium ion battery positive electrode material precursor is 2% -20%. The carbonate precursor is prevented from growing continuously, in particular, the seed crystal can be added for a small amount for multiple times, and under the same condition, if more carbonate precursor is added in each batch, the adding times can be properly reduced; in addition, under the same conditions, if the difference between the particle diameter of the seed crystal and the preset particle diameter is large, the amount of the seed crystal to be added may be relatively reduced, and if the difference between the particle diameter of the seed crystal and the preset particle diameter is small, the amount of the seed crystal to be added needs to be relatively increased.
In some embodiments, the method comprises: and (3) adding the salt solution and the carbonate solution of the metal element into the base solution in parallel, performing coprecipitation reaction, and adding the seed crystal into the reaction system in batches each time the precipitated D50 reaches the preset particle size.
According to the embodiment, the seed crystal is introduced on the basis of the original coprecipitation process, so that the controllability of the coprecipitation process is improved.
Ammonia may be introduced as a complexing agent while facilitating maintenance of pH at the time of precipitation. In particular, the ammonia concentration may be 0g/L, 2g/L, 4g/L, 6g/L, 8g/L, or any value between 0g/L and 8 g/L.
In some embodiments, the concentration of ammonia (calculated by NH 3) in the reaction solution is kept to be 0.1g/L-8g/L during the coprecipitation reaction, specifically, any value between 0.1g/L, 0.3g/L, 0.5g/L, 1g/L, 3g/L, 8g/L or 0.1g/L-8g/L can be used, under the same condition, the ammonia concentration is too high, the reaction speed is too slow, the efficiency is not improved, the ammonia concentration is too low, the precipitation is too fast, and the density of particles can be reduced. In some embodiments, the ammonia concentration of the aqueous ammonia fed into the reaction solution may be 12g/L to 25g/L.
In some embodiments, the total concentration of the metal elements in the salt solution of the metal elements is 0.1mol/L to 2.5mol/L, specifically may be 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or any value between 0.1mol/L and 1mol/L and 2.5mol/L, and in some embodiments, the total concentration of the metal elements in the salt solution of the metal elements is 1.7mol/L to 2.0mol/L. The concentration of the metal elements can influence the speed of coprecipitation, the size, the shape and the like of the obtained precipitate, if the total concentration of the metal elements is too high, the precipitation speed is too high, the control of the precipitation process is not facilitated, and loose particles are easy to obtain; if the total concentration of the metal elements is too small, the precipitation speed is too slow, which is unfavorable for improving the production efficiency.
In some embodiments, the salt solution flow acceleration of the metal element is 1L/h-20L/h, and specifically may be 1L/h, 5L/h, 10L/h, 15L/h, 20L/h, or any value between 1L/h-8L/h, 8L/h-12L/h, 12L/h-20L/h. Likewise, the salt solution of the metal element has too high flow acceleration, the coprecipitation speed is too high, the control of the precipitation process is not facilitated, and loose particles are easy to obtain; if the flow acceleration of the salt solution of the metal element is too small, the precipitation speed is too slow, which is favorable for improving the density of the precipitated particles, but is unfavorable for improving the production efficiency.
In some embodiments, the carbonate solution has a concentration of 0.1mol/L to 1.8mol/L, specifically may be any value between 0.1mol/L, 0.3mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 1.8mol/L, or 0.1mol/L to 1.8mol/L, and in some embodiments, the carbonate solution has a concentration of 1.5mol/L to 1.8mol/L. If the concentration of the carbonate solution is too high, the precipitation speed is too high, the control of the precipitation process is not facilitated, and loose particles are easy to obtain; if the concentration of the carbonate solution is too small, the precipitation speed is too slow, which is unfavorable for improving the production efficiency.
In some embodiments, the carbonate solution has a flow acceleration of 8L/h to 12L/h, and specifically may be 8L/h, 9L/h, 10L/h, 11L/h, 12L/h, or any value between 8L/h and 12L/h. Likewise, carbonate solutions are too fast in flow, co-precipitation is too fast, which is detrimental to control of the precipitation process, and loose particles are easily obtained; if the flow acceleration of the carbonate solution is too small, the precipitation speed is too slow, which is beneficial to improving the density of the precipitated particles, but is not beneficial to improving the production efficiency.
In some embodiments, the base fluid further comprises ammonia water, and the concentration of ammonia in the base fluid is 0g/L-8g/L, specifically can be 0g/L, 2g/L, 4g/L, 6g/L, 8g/L or any value between 0g/L and 8 g/L. In some embodiments, the ammonia concentration is 2g/L to 4g/L. Ammonia water is added into the base solution, which is favorable for controlling the precipitation speed and obtaining precursor particles with better sphericity.
In some embodiments, the base fluid further comprises carbonate, wherein the concentration of carbonate in the base fluid is from 0.01mol/L to 1.5mol/L.
In some embodiments, the coprecipitation reaction is carried out under inert gas protection, and the inert gas may be nitrogen, argon, etc., and nitrogen is usually selected to avoid oxidation of the reactants.
In some embodiments, the pH of the coprecipitation step is 8-11, and in particular may be any value between 8, 9, 10, 11 or 8-11, in some embodiments 9.5-10, which is advantageous for precursor nucleation and growth.
In some embodiments, the temperature of the coprecipitation reaction is from 30 ℃ to 70 ℃, specifically can be any value between 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, or 30 ℃ to 70 ℃, which ranges to facilitate precursor nucleation and growth.
In some embodiments, the coprecipitation reaction is carried out under stirring conditions, the stirring frequency being 30Hz to 60Hz, in particular it may be 30Hz, 40Hz, 50Hz, 60Hz or any value between 30Hz and 60 Hz.
On one hand, the stirring in the embodiment can lead the distribution of materials in the reaction liquid to be relatively uniform, and the improvement of the stirring speed is beneficial to the uniform distribution of products; on the other hand, during stirring, collision and friction can be generated among particles in a reaction system, the stirring speed is too high, and continuous collision among the particles can cause the particles to be broken, cracked and the like, so that the quality of precursor particles is not improved, and the stirring speed is not too high.
In some embodiments, the seed crystals are added in batches over 2h-5h, in particular, the time may be controlled to be any value between 2h, 3h, 4h, 5h, or 2h-5 h. In general, if the particle size of the seed crystal and D50 of the preset precipitate differ greatly, the amount of seed crystal added can be relatively reduced, and the time between the first seed crystal addition and the last seed crystal addition can be relatively shortened; if the grain diameter of the seed crystal is smaller than the preset grain diameter, the adding amount of the seed crystal needs to be relatively increased, and the time for adding the seed crystal is prolonged.
In some embodiments, further comprising the preparation of seed crystals: and (3) introducing ammonia water into the salt solution of the metal element, adjusting the pH value of the reaction solution by adopting alkali liquor, and synthesizing the seed crystal.
According to the prior art, taking copper as an example, the copper-based multi-component hydroxide precursor has inconsistent precipitation rate due to the difference of Cu ions K SP and other ions, so that segregation phenomenon occurs, and uniform precipitation is difficult, but in the embodiment, the seed crystal accounts for only 2% -3%, the seed crystal accounts for relatively small, and the influence on the overall performance of the precursor is relatively small.
In some embodiments, the ammonia concentration in the reaction solution is kept to be 2g/L-4g/L in the preparation step of the seed crystal, specifically, the ammonia water can be any value between 2g/L, 3g/L, 4g/L or 2g/L-4g/L, and the ammonia water is used as a complexing agent, so that the control of the precipitation speed is facilitated, and the seed crystal with better sphericity is facilitated to be obtained.
The concentration of ammonia in the reaction solution is increased to facilitate the production of finer crystal grains, so that the concentration of ammonia in the reaction solution can be slightly higher than that in the reaction solution during the precipitation of carbonate when the seed crystal is prepared.
In some embodiments, the pH of the reaction solution is maintained in the range of 8-13, in particular, any value between 8, 9, 10, 11, 12, 13 or 8-13, during the seed crystal preparation step, which is advantageous for seed crystal nucleation and growth.
In some embodiments, the seed crystal may be prepared at a step temperature of 30 ℃ to 70 ℃, specifically 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, or any value between 30 ℃ and 70 ℃, which range facilitates seed crystal nucleation and growth.
In some embodiments, the lye is sodium hydroxide solution or potassium hydroxide solution, the lye concentration is 5mol/L-10mol/L, in particular may be 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L or any value between 5mol/L and 10mol/L, mainly for adjusting the pH of the solution.
In some embodiments, the seed preparation step is performed under stirring conditions at a frequency of 30Hz to 60Hz, in particular 30Hz, 40Hz, 50Hz, 60Hz or any value between 30Hz and 60 Hz.
On one hand, the stirring in the embodiment can lead the distribution of materials in the reaction liquid to be relatively uniform, and the improvement of the stirring speed is beneficial to the uniform distribution of products; on the other hand, during stirring, collision and friction can be generated among particles in a reaction system, the stirring speed is too high, and continuous collision among the particles can cause the particles to be broken, cracked and the like, so that the quality of precursor particles is not improved, and the stirring speed is not too high.
The embodiment of the disclosure provides a positive electrode material, which is obtained by mixing and sintering the sodium ion battery positive electrode material precursor and a sodium source according to any one of the previous embodiments.
The embodiment of the disclosure provides a positive electrode plate, which comprises the positive electrode material in the previous embodiment.
The embodiment of the disclosure provides a sodium ion battery, which comprises the positive electrode plate in the previous embodiment.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a precursor of a positive electrode material of a sodium ion battery, which specifically comprises the following steps:
(1) Preparation of Ni 0.3Mn0.50Fe0.1Cu0.1(OH)2 seed crystal: introducing Ni into a reaction kettle according to the following proportion: mn: fe: the molar ratio of Cu is 0.3:0.50:0.1:0.1, corresponding nickel sulfate, manganese sulfate, ferrous sulfate and copper sulfate raw materials are weighed to prepare metal liquid with the total concentration of metal elements of 2mol/L, ammonia water is introduced, the concentration of ammonia in a kettle is always kept to be 2g/L, liquid alkali is introduced to adjust the pH value to be 10.5, and small particle seed crystals with the D50 of 5 mu m are prepared.
(2) Synthesis of precursor materials:
s1, sodium carbonate configuration: according to the experimental requirements, a sodium carbonate solution with a concentration of 1.8mol/L is prepared.
S2, bottom solution of the reaction kettle: adding 1/3 of pure water into a reaction kettle with the volume of 500L, heating to 65 ℃, introducing N 2, adding sodium carbonate into the bottom solution of the reaction kettle to make the concentration of the sodium carbonate be 0.08mol/L, and starting stirring to be 50Hz.
S3, after experimental conditions in the kettle are met, 10L/h of the metal liquid prepared in the step 1 is introduced, meanwhile, ammonia water is introduced to keep the ammonia concentration in the kettle to be 0.5g/L, and 1.8mol/L of sodium carbonate solution is introduced to adjust the pH value to 9.5, so that nucleation growth is carried out; when the particle D50 of the precipitated particles reaches 10 mu m, the seed crystal prepared in the step (1) is thrown in batches, the particle D50 in the kettle is continuously controlled to be 10 mu m until the expected yield is reached to 200Kg, the total mass of the finally thrown seed crystal is 10Kg, and the precursor material with good granularity consistency and good sphericity and mainly comprising the carbonate precursor of Ni 0.3Mn0.50Fe0.1Cu0.1CO3 is prepared, and an electron microscope diagram is shown in figure 1.
Comparative example 1
The difference between comparative example 1 and example 1 is that: in comparative example 1, no Ni 0.3Mn0.50Fe0.1Cu0.1(OH)2 seed crystal is added, and when the D50 reaches 10 mu m, a precursor material mainly comprising Ni 0.3Mn0.50Fe0.1Cu0.1CO3 carbonate precursor is obtained, and an electron microscope image is shown as a figure 2, wherein the obtained carbonate precursor has uneven particle size distribution, poor sphericity and uncontrollable particle size.
Example 2
The embodiment provides a preparation method of a precursor Ni 0.2Mn0.40Fe0.2Cu0.2CO3 of a positive electrode material of a sodium ion battery, which specifically comprises the following steps:
(1) Preparation of Ni 0.2Mn0.40Fe0.2Cu0.2(OH)2 seed crystal: introducing Ni into a reaction kettle according to the following proportion: mn: fe: the molar ratio of Cu is 0.2:0.40:0.2:0.2, corresponding nickel sulfate, manganese sulfate, ferrous sulfate and copper sulfate raw materials are weighed to prepare metal liquid with the total concentration of metal elements of 2mol/L, ammonia water is introduced to keep the concentration of ammonia in a kettle at 2g/L all the time, liquid alkali is introduced to adjust the pH value to 10.5, and small particle seed crystals with the D50 of 4 mu m are prepared.
(2) Synthesis of precursor materials:
s1, sodium carbonate configuration: according to the experimental requirements, a sodium carbonate solution with a concentration of 1.8mol/L is prepared.
S2, bottom solution of the reaction kettle: adding 1/3 of pure water into a reaction kettle with the volume of 500L, heating to 70 ℃, introducing N 2, adding sodium carbonate into the bottom solution of the reaction kettle to enable the concentration of the sodium carbonate to be 0.08mol/L, and starting stirring to be 45Hz.
S3, after experimental conditions in the kettle are met, 10L/h of the metal liquid prepared in the step 1 is introduced, meanwhile, ammonia water is introduced to keep the ammonia concentration in the kettle to be 0.5g/L, and 1.8mol/L of sodium carbonate solution is introduced to adjust the pH value to 9.5, so that nucleation growth is carried out; and (3) when the D50 reaches 12 mu m, adding the prepared seed crystal in batches, continuously controlling the particle D50 in the kettle to be 12 mu m until the expected yield is 200Kg, and finally adding the seed crystal to be 20Kg in total mass to prepare the precursor material with the main carbonate precursor of Ni 0.2Mn0.40Fe0.2Cu0.2CO3 with good granularity consistency.
Example 3
The embodiment provides a preparation method of a precursor Ni 0.25Mn0.25Fe0.25Cu0.25CO3 of a positive electrode material of a sodium ion battery, which specifically comprises the following steps:
(1) Preparation of Ni 0.25Mn0.25Fe0.25Cu0.25(OH)2 seed crystal: introducing Ni into a reaction kettle according to the following proportion: mn: fe: the molar ratio of Cu is 0.25:0.25:0.25:0.25.25, corresponding nickel sulfate, manganese sulfate, ferrous sulfate and copper sulfate raw materials are weighed to prepare metal liquid with the total concentration of metal elements of 1.7mol/L, ammonia water is introduced to always keep the concentration of ammonia in a kettle to be 4g/L, liquid alkali is introduced to adjust the pH value to be 10.5, and small particle seed crystals with the D50 of 4 mu m are prepared.
(2) Synthesis of precursor materials:
s1, sodium carbonate configuration: according to the experimental requirements, a sodium carbonate solution with a concentration of 1.8mol/L is prepared.
S2, bottom solution of the reaction kettle: adding 1/3 of pure water into a reaction kettle with the volume of 500L, heating to 60 ℃, introducing N 2, adding sodium carbonate into the bottom solution of the reaction kettle to make the concentration of the sodium carbonate be 1.2mol/L, and starting stirring to be 45Hz.
S3, after experimental conditions in the kettle are met, starting to introduce 8L/h of the metal liquid prepared in the step 1, simultaneously introducing ammonia water to keep the ammonia concentration in the kettle to be 2g/L, and introducing 1.8mol/L of sodium carbonate solution to adjust the pH value to 9.5, so as to carry out nucleation growth; when the precipitated particles D50 reach 8 mu m, the seed crystal prepared in the step (1) is thrown in batches, the particles D50 in the kettle are continuously controlled to be 8 mu m until the expected yield is 200Kg, and finally the total mass of the thrown seed crystal is 15Kg, so that the precursor material with the main carbonate precursor of Ni 0.25Mn0.25Fe0.25Cu0.25CO3 with better granularity consistency is prepared.
Example 4
The embodiment provides a preparation method of a precursor Ni 0.20Mn0.20Fe0.30Cu0.30CO3 of a positive electrode material of a sodium ion battery, which specifically comprises the following steps:
(1) Preparation of Ni 0.20Mn0.20Fe0.30Cu0.30(OH)2 seed crystal: introducing Ni into a reaction kettle according to the following proportion: mn: fe: the molar ratio of Cu is 0.20:0.20:0.30:0.30, corresponding nickel sulfate, manganese sulfate, ferrous sulfate and copper sulfate raw materials are weighed to prepare metal liquid with the total concentration of metal elements of 1.7mol/L, ammonia water is introduced to keep the concentration of ammonia in a kettle at 4g/L all the time, liquid alkali is introduced to adjust the pH value to 10.5, and small particle seed crystals with the D50 of 4 mu m are prepared.
(2) Synthesis of precursor materials:
s1, sodium carbonate configuration: according to the experimental requirements, a sodium carbonate solution with a concentration of 1.8mol/L is prepared.
S2, bottom solution of the reaction kettle: adding 1/3 of pure water into a reaction kettle with the volume of 500L, heating to 60 ℃, introducing N 2, adding sodium carbonate into the bottom solution of the reaction kettle to make the concentration of the sodium carbonate be 0.04mol/L, and starting stirring to be 45Hz.
S3, after experimental conditions in the kettle are met, starting to introduce 12L/h of the metal liquid prepared in the step 1, and simultaneously introducing 1.8mol/L of sodium carbonate solution to adjust the pH value to 9.5, and carrying out nucleation growth; when the precipitated particles D50 reach 8 mu m, the seed crystal prepared in the step (1) is thrown in batches, the particles D50 in the kettle are continuously controlled to be 8 mu m until the expected yield is 200Kg, and finally the total mass of the thrown seed crystal is 15Kg, so that the precursor material with the main carbonate precursor of Ni 0.20Mn0.20Fe0.30Cu0.30CO3 with better granularity consistency is prepared.
Example 5
The embodiment provides a preparation method of a precursor Ni 0.333Mn0.333Fe0.333CO3 of a positive electrode material of a sodium ion battery, which specifically comprises the following steps:
(1) Preparation of Ni 0.33Mn0.33Fe0.33(OH)2 seed crystal: introducing Ni into a reaction kettle according to the following proportion: mn: the molar ratio of Fe is 0.33:0.33:0.33, corresponding nickel sulfate, manganese sulfate and ferrous sulfate raw materials are weighed to prepare metal liquid with the total concentration of metal elements of 1.7mol/L, ammonia water is introduced to keep the concentration of ammonia in a kettle at 4g/L all the time, liquid alkali is introduced to adjust the pH value to 10.5, and small particle seed crystals with the D50 of 4 mu m are prepared.
(2) Synthesis of precursor materials:
s1, sodium carbonate configuration: according to the experimental requirements, a sodium carbonate solution with a concentration of 1.8mol/L is prepared.
S2, bottom solution of the reaction kettle: adding 1/3 of pure water into a reaction kettle with the volume of 500L, heating to 60 ℃, introducing N 2, adding sodium carbonate into the bottom solution of the reaction kettle to make the concentration of the sodium carbonate be 1mol/L, and starting stirring to be 45Hz.
S3, after experimental conditions in the kettle are met, starting to introduce 12L/h of the metal liquid prepared in the step 1, and simultaneously introducing 1.8mol/L of sodium carbonate solution to adjust the pH value to 9.5, and carrying out nucleation growth; when the precipitated particles D50 reach 8 mu m, the seed crystal prepared in the step (1) is thrown in batches, the particles D50 in the kettle are continuously controlled to be 8 mu m until the expected yield is 200Kg, and finally the total mass of the thrown seed crystal is 12Kg, so that the precursor material with the main carbonate precursor of Ni 0.33Mn0.33Fe0.33CO3 and good granularity consistency is prepared.
Example 6
The only difference from example 1 is that small particle seeds with a D50 of 2 μm were prepared in step (1).
Example 7
The only difference from example 1 is that small particle seeds with a D50 of 8 μm were prepared in step (1).
Example 8
The only difference from example 1 is that in step (2) a carbonate precursor having a D50 of 20 μm was prepared.
Example 9
The only difference from example 1 is that the final seed mass charged in step (2) was 5Kg. As can be seen from the data in the following table, the seed charge amount was reduced, the particle size control effect was weaker, and the particle size distribution was wider than in example 1.
Example 10
The only difference from example 1 is that the final seed mass charged in step (2) was 20Kg. As can be seen from the data in the table below, too much seed addition results in too many small particles of seed, and an increase in small particle size, as well as a broad particle size distribution, compared to example 1.
The carbonate precursors obtained in the above examples and comparative examples were tested for particle size distribution, tap density, and specific surface area, and the test results are shown in the following table.
Industrial applicability
The main component of the sodium ion battery positive electrode material precursor in the embodiment is a carbonate precursor, and a small amount of hydroxide precursor is also introduced, so that the introduction of the hydroxide precursor is beneficial to controlling the particle size distribution of the precursor in the precursor preparation process, narrowing the particle size distribution of the carbonate precursor and further improving the tap density of the precursor.

Claims (10)

1. The sodium ion battery positive electrode material precursor is characterized by comprising first precursor particles and second precursor particles, wherein the first precursor particles are carbonate precursors, the second precursor particles comprise a core and a shell, the core is a hydroxide precursor, and the shell is a carbonate precursor.
2. The sodium ion battery positive electrode material precursor according to claim 1, wherein the hydroxide precursor accounts for 2% -20% of the total mass of the sodium ion battery positive electrode material precursor;
and/or the precursor D50 of the positive electrode material of the sodium ion battery is 5-20 mu m;
And/or the D50 of the core is 2-8 μm;
And/or the metal element in the carbonate precursor and/or the hydroxide precursor is one or a combination of more than two kinds of Li, K, al, ti, cr, mn, fe, cu, co, ni, zn, sn, zr, mo, nb, Y, W, in, ge.
3. A method for preparing the precursor of the positive electrode material of the sodium ion battery as claimed in claim 1 or 2, comprising: in the process of preparing carbonate precursor particles by adopting a coprecipitation method, hydroxide precursors are used as seed crystals, and the particle size distribution of the carbonate precursor particles is regulated to obtain the sodium ion battery anode material precursor.
4. The method for preparing a precursor of a sodium ion battery cathode material according to claim 3, wherein in the process of preparing carbonate precursor particles by adopting a coprecipitation method, the seed crystal is added into a reaction system every time the D50 obtained by precipitation reaches a preset particle size, and the total mass fraction of the seed crystal in the precursor of the sodium ion battery cathode material is 2% -20%.
5. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 3, comprising: adding a salt solution and a carbonate solution of metal elements into a base solution in parallel, performing coprecipitation reaction, and adding the seed crystal into a reaction system in batches each time when the D50 of precipitation reaches a preset particle size;
Preferably, ammonia water is added into the bottom liquid in a flowing way; more preferably, the ammonia concentration in the reaction liquid is kept to be 0.1g/L-8g/L during the coprecipitation reaction;
preferably, the total concentration of the metal elements in the salt solution of the metal elements is 0.1mol/L to 2.5mol/L;
Preferably, the total concentration of the metal elements in the salt solution of the metal elements is 1.7mol/L to 2.0mol/L;
preferably, the salt solution flow acceleration of the metal element is 1L/h-20L/h;
Preferably, the concentration of the carbonate solution is 0.1mol/L to 1.8mol/L;
Preferably, the concentration of the carbonate solution is 1.5mol/L to 1.8mol/L;
Preferably, the flow acceleration of the carbonate solution is 8L/h-12L/h;
Preferably, the base solution also contains ammonia water, and the concentration of the ammonia in the base solution is 0g/L-8g/L;
Preferably, the base solution also contains carbonate, and the concentration of the carbonate in the base solution is 0.01mol/L-1.5mol/L;
preferably, the coprecipitation reaction is carried out under inert gas protection;
preferably, the pH of the coprecipitation step is 8-11;
Preferably, the temperature of the coprecipitation reaction is 30 ℃ to 70 ℃;
preferably, the coprecipitation reaction is carried out under stirring conditions, and the stirring frequency is 30Hz-60Hz;
preferably, the seed crystals are added in batches over a period of 2h-5 h.
6. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 3, further comprising the preparation of a seed crystal: ammonia water is introduced into the salt solution of the metal element, and alkali liquor is adopted to adjust the pH value of the reaction solution so as to synthesize the seed crystal.
7. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 6, wherein the concentration of ammonia in the reaction solution is kept at 2g/L to 4g/L in the step of preparing the seed crystal;
And/or, maintaining the pH value of the reaction solution in the range of 8-13 in the preparation step of the seed crystal;
and/or the preparation step temperature of the seed crystal is 30-70 ℃;
And/or the alkali liquor is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the alkali liquor is 5mol/L-10mol/L;
and/or the seed crystal preparation step is carried out under stirring condition, and the stirring frequency is 30Hz-60Hz.
8. A positive electrode material, which is obtained by mixing and sintering the precursor of the positive electrode material of the sodium ion battery according to any one of claims 3 to 7 with a sodium source.
9. A positive electrode sheet comprising the positive electrode material according to claim 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
CN202410167092.6A 2024-02-06 2024-02-06 Sodium ion battery anode material precursor, preparation method and application Pending CN117985779A (en)

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